Process for preparing polyol-catalyst mixtures useful in the preparation of rigid polyurethane cellular products

ABSTRACT

Polyol-catalyst mixtures, useful in the preparation of rigid polyurethane cellular products, are prepared simultaneously by reacting a Mannich base compound, water, and an epoxide and subsequently removing the water from the reaction mixture. Also provided are new rigid polyurethane cellular products having a high content of isocyanurate linkages, superior heat distortion temperatures and improved insulating properties, which products are obtained by reacting a polyisocyanate with the aforementioned polyol-catalyst mixture.

This is a division, of application Ser. No. 335,947, filed 12/30/81 andnow U.S. Pat. No. 4,404,121, issued Sept, 13, 1983.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new process for preparing polyol-catalystmixtures. More particularly, the invention relates to a new process forpreparing polyol-catalyst mixtures which are useful in the preparationof improved rigid polyurethane cellular products.

Specifically, the invention provides a new process for simultaneouslypreparing a polyol-catalyst mixture which can be used to produceimproved rigid polyurethane cellular products, which process comprisesreacting a Mannich base compound, water and an epoxide, such as ethyleneoxide, together at an elevated temperature, and subsequently removingthe water from the reaction mixture. The invention further provides newand valuable polyurethanes, and particularly new rigid polyurethanecellular products having a high content of isocyanurate linkages,improved heat distortion temperatures and improved insulatingproperties, which products are prepared by reacting the aforementionedpolyol-catalyst mixture with a polyisocyanate.

2. Description of the Prior Art

It is known to prepare rigid polyurethane foams by the reaction of apolyisocyanate with a hydroxyl-terminated polyester, polyether orpolyamine, which generally have hydroxyl numbers within the range offrom about 350 to 900. However, to date no ideal polyol has been foundand, for various reasons, polyurethane foams prepared from such polyolshave not been entirely satisfactory.

Still further, the production of a satisfactory urethane foam requiresthat the relative rates of the various reactions that occur be properlybalanced. This balance is normally obtained by careful selection of acatalyst system. The catalyst usually consists of a tertiary amine usedalone or, when necessary, mixed with organic tin compounds in a mannerwell known to those skilled in the art. The tertiary amines so employedwill normally impart an objectionable odor to the final foam product.

U.S. Pat. No. 3,297,597 proposes the use of certain nitrogen-containingpolyols which act both as a polyol and a catalyst in the reaction withthe polyisocyanates. This avoids some of the difficulties noted above,such as the odor of the amine catalyst, but still retains some of thelimitations of the prior known products, such as limited heatresistance, limited compatibility and limited isocyanurate linkagesretained in the cured product.

It is an object of the invention, therefore, to provide a new processfor preparing polyol-catalyst mixtures useful in the preparation ofpolyurethane foams. It is a further object to provide a process forpreparing new polyol-catalyst mixtures which impart many improvements tothe preparation of rigid polyurethane cellular products. It is a furtherobject to provide new polyol-catalyst mixtures for polyurethane foampreparation which permit the production of products having a highernumber of isocyanurate linkages. It is a further object to provide newpolyol-catalyst mixtures for polyurethane production which permitsslower and more desirable reaction. It is a further object to providenew polyol-catalyst mixtures which give polyurethane foamed productshaving improved heat resistance and insulation properties. It is afurther object to provide new polyol-catalyst mixtures which have bettercompatibility with the reaction components. It is a further object toprovide new polyol-catalyst mixtures which are simple and economical toprepare. These and other objects of the invention will be apparent fromthe following detailed description thereof.

SUMMARY OF THE INVENTION

It has now been discovered that these and other objects may beaccomplished by the new polyol-catalyst mixtures of the presentinvention which are prepared in good yield by reacting a Mannich basecompound, water and an epoxide, such as ethylene oxide, together at anelevated temperature, and then removing the water from the reactionmixture. It was surprising to find that polyol-catalyst mixtures havingsuperior properties could be obtained by this straightforward economicalprocess. It was found, for example, that the new polyol-catalystmixtures formed in this manner had excellent compatibility with theingredients used in the formation of polyurethane foams. In addition,the new polyol-catalyst mixtures permit better control over the rate ofreaction and yielded improved products. The products so prepared, forexample, have a higher number of isocyanurate linkages and greatlyimproved heat resistance properties as well as excellent insulatingproperties. The production of products having these improved propertiesis illustrated in the examples at the end of the specification.

DETAILED DESCRIPTION OF THE INVENTION

The process for producing the new polyol-catalyst mixtures having theimproved properties is made up of the following steps:

(a) mixing a Mannich base compound, water and an epoxide, such asethylene oxide, together in a reaction chamber and heating the mixtureto a temperature below about 150° C. and,

(b) subsequently stripping the water from the reaction mixture.

The process for using the above noted polyol-catalyst mixtures in thepreparation of improved rigid polyurethane cellular products comprisesreacting the said polyol-catalyst mixture with the desiredpolyisocyanate and other components, such as blowing agent, stabilizer,fire-retardant, etc. in the desired proportions.

In order to present the inventive concept of the present invention inthe greatest possible detail, the following supplementary disclosure issubmitted.

The Mannich base used in the preparation of the new polyol-catalystmixtures are prepared by reacting a phenolic compound with formaldehydeand an alkanolamine. The Mannich reaction is conducted by premixing thephenolic compound with a desired amount of the alkanolamine and thenslowly adding formaldehyde to the mixture at a temperature below thetemperature of Novolak formation (a temperature that will vary with thephenolic compound employed and is a temperature of less than about 35°C. when phenol itself is employed). At the end of the formaldehydeaddition, the reaction mixture is slowly heated with agitation to atemperature of at least about 50° C. such as a temperature within therange of about 80° C. to 150° C. for a period of time sufficient toreduce the formaldehyde content to at least about 1 wt percent. Thiswill normally require from about two to about four hours reaction timeat the elevated temperature.

The phenolic compound to be employed in the Mannich condensation is anaromatic compound containing one or more hydroxyl groups attacheddirectly to the aromatic nucleus and having a hydrogen atom on one ormore of the ring positions ortho and para to the hydroxyl group andwhich is otherwise unsubstituted or substituted with substituents whichare nonreactive under Mannich reaction conditions. Substituent groupsthat may be present include alkyl, cycloalkyl, aryl, halo, nitro,carboalkoxy, haloalkyl and hydroxyalkyl. The phenolic compound isfurther characterized by a molecular weight within the range of fromabout 94 to about 500. Examples of acceptable phenolic compoundsinclude, among others, o-, m-, or p-cresols, ethylphenol, nonylphenol,p-phenylphenol, 2,2-bis(4-hydroxyphenyl)propane, beta-naphthol,beta-hydroxyanthracene, p-chlorophenol, o-bromophenol, 2,6-chlorophenol,p-nitrophenol, 4-nitro-6-phenylphenol, 3,5- dimethylphenol,p-isopropylphenol, 2-bromo-4-cyclohexylphenol,2-(4-hydroxyphenyl)ethanol, and 4-chlorophenol.

The alkanolamine to be reacted with the phenolic compound andformaldehyde in accordance with the method of making the Mannich basesis an alkanolamine and preferably those of the formula ##STR1## whereinR is hydrogen or an alkyl radical preferably containing 1 to 4 carbonatoms, at least one R₁ or R₂ is hydrogen and the remaining R₁ or R₂ ishydrogen or a hydrocarbon or substituted hydrocarbon radical and n is aninteger, preferably 2 to 6.

Examples of suitable alkanolamines that may be used aremonoethanolamine, diethanolamine, isopropanolamine,bis(2-hydroxypropyl)amine, hydroxyethylmethylamine,N-hydroxyethylpiperazine, N-hydroxybutylamine,N-hydroxyphenyl-2,5-dimethylpiperazine, etc.

Formaldehyde may be employed in the Mannich reaction in any of itsconventional forms, such as an aqueous formalin solution, an inhibitedmethanol solution, paraformaldehyde, or trioxane.

The proportions of reactants used in making the Mannich bases may varyover a wide range depending upon the type of product desired. Forexample, if phenol, diethanolamine and formaldehyde are employed in amolar ratio of 1:3:3, the predominant product will have seven hydroxylgroups attached to a single molecule. If the molar ratio of these samereactants is changed to 1:2:2, a pentol will be obtained as thepredominant product. Similarly, when the molar ratio is 1:1:1, a triolis the predominant product. If an excess of formaldehyde is used inpreparing the triol or pentol, the Mannich reaction becomes complex dueto the secondary condensation of phenol with formaldehyde.

The Mannich products possess a plurality of hydroxy-terminated sidechains available for further reaction with the epoxide. The preferredMannich products may be represented by the following formula ##STR2##wherein the R₁ 's represent hydrogen or a --CH₂ N(XOH)₂ radical whereinX is an alkylene radical containing up to 8 carbon atoms. The productprepared from phenol, diethanolamine and formaldehyde in a 1:3:3 ratiomay be represented by the formula ##STR3##

The exact structure of the Mannich bases will depend upon the proportionof reactants employed but they will all possess a plurality of activehydroxy-terminated side chains. A detailed description of thepreparation of suitable Mannich bases may be found in U.S. Pat. No.3,297,597.

As noted in U.S. Pat. No. 3,297,597, water is formed in the reaction andin that particular case, special care is taken to remove the water asnoted in col. 2, line 34 of that patent. However, in the presentprocess, the water is not removed but retained in the reaction toparticipate in the reaction with the alkylene oxide. For desiredresults, the amount of water to be retained in the reaction mixtureshould be at least 2% by weight, and preferably between 5% and 25% byweight.

As noted above, the new polyol-catalyst mixtures are obtained byreacting the above-noted Mannich bases with water and an epoxide, andpreferably an alkylene oxide. The epoxide to be used include the mono-and polyepoxides, and particularly those of the formula ##STR4## whereinboth Rs can be hydrogen or an organic radical, preferably containing upto 12 carbon atoms. Examples of the epoxides include, among others,butadiene monoepoxide, epichlorohydrin, styrene oxide, ethylene oxide,propylene oxide, butylene oxide, cyclohexeneoxide, epoxpropylbenzene,epoxypropylnapthalene, 1,2,5-triepoxypropylbenzene, and the like, andmixtures thereof. Particularly preferred are the aliphatic monoepoxidescontaining 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide,butylene oxide, amylene oxide.

The amount of the epoxide to be used in the preparation process may varyover a wide range. In general, the amount of the alkylene oxide may varyfrom about 1 to 10 times the amount of the Mannich base, but should besufficient to react with a majority of the --XOH groups in the Mannichbase. Preferably the epoxide is employed in amounts varying from about 2to 6 moles per mole of Mannich base.

The Mannich base, water and epoxide can be combined in any order but itis generally preferred to add the epoxide to the reaction mixturecontaining the Mannich base and water. Temperatures employed in theprocess may vary within a wide range. In general, it is desirable tomaintain the temperature below about 150° C., and more preferablybetween about 90° C. and 125° C. Atmospheric, superatmospheric orsubatmospheric pressures may be utilized as desired or necessary.

The heat is continued until the desired polyol-catalyst mixture isobtained. In general, this is accomplished with reaction periods varyingfrom about 0.5 hour to about 3 hours, depending upon the nature of thereactants and the temperature employed.

At the conclusion of the reaction, the water and other low molecularweight products such as excess epoxide are stripped from the reactionmixture. This is preferably accomplished by distillation under highvacuum.

The polyol-catalyst mixtures prepared by the above process may berecovered as liquids or soft solids. They will preferably have ahydroxyl number varying from about 300 to 1000, an amine content varyingfrom 2 to 3 meg/g., color as determined by the Gardner scale of about 8to 15 and a pH varying from about 10 to about 12.5.

As noted above, the new polyol-catalyst composition produced as aboveare particularly valuable in the reaction with isocyanates to formpolyurethanes or polyisocyanurates. They are particularly outstanding inthe reaction with polyisocynates to form rigid cellular polyurethanesthat have greatly improved properties. In this reaction they arecombined with desired polyisocyanate and other components generally usedin the formation of cellular products, such as blowing agents, fireretardants, stabilizers, etc., and the reaction effected by use of knowntechniques.

The polyisocyanates to be used in making the foams of the presentinvention include those compounds containing at least two isocyanategroups per molecule, such as, for example, tolylene diisocyanate (TDI),hexamethylenediisocyanate, chlorophenyldiisocyanate,bromophenyldiisocyanate, tetraisocyanatodiphenylmethane,3,3'-dichloro-4,4'-biphenyldiisocyanate, diphenol diisocynate, ehtylenediisocyanate, propylene 1,2-diisocyanate, 1,4-tetramethylenediisocyanate, p-phenylene diisocyanate, polymethylenepolyphenylisocyanate, and mixtures thereof. Preferred polyisocyanatesinclude the organic aromatic, aliphatic or cycloaliphaticpolyisocyanates. Coming under special consideration are the prepolymersobtained by reacting active hydrogen containing compounds, such asalcohols or amines with excess polyisocyanates, which polymers contain aplurality of free isocyanate groups such as from 3 to 8 such groups.

Also of special consideration are the aromatic polyisocyanates such as,for example, 2,4- and 2,6-toluene diisocyanates and methylene-bridgedpolyphenyl polyisocyanate mixtures which have a functionality of fromabout 2 to about 4. These latter isocyanates compounds are generallyproduced by the phosgenation of corresponding methlyene-bridgedpolyphenyl polyamines. Most preferred methylene-bridged polyphenylpolyisocyanates mixtures contain about 20 to 100 weight percentmethylene diphenyldiisocyanate isomer, with the remainder beingpolymethylene polyphenyl polyisocyanates having higher functionality andhigher molecular weights.

The most commonly used foam stabilizers are silicone oils, usuallysilicone-glycol copolymers such as those prepared in accordance with thedisclosure of U.S. Pat. No. 2,834,748. Such materials have the formula

    R'Si(O--(R.sub.2 SiO).sub.n --(oxyalkylene).sub.m R")s

wherein R, R' and R" are alkyl groups containing 1 to 4 carbon atoms, nis 4 to 8, m is 20 to 40, and the oxyalkylene groups are derived fromethylene and propylene oxides or mixtures thereof.

Blowing agents used to prepare rigid urethane foams are generallyvolatile liquids such as, for example, trichlorofluoromethane.

Fire retardants that can be incorporated in the foaming mixture are oftwo types, those that are incorporated by mere mechanical mixing andthose that become chemically bound in the polymer chains. The mostcommonly used of the first type are tris(chloroethyl) phosphate andtris(chloropropyl) phosphate. The second type of fire retardant offersanother approach to the problem of fire retarding foams. Examples ofthis type include chlorendic acid derivatives, terephthalatederivatives, and various phosphorus-containing polyols.

While the new cellular polyurethane products of the present inventionare obtained by using the new polyol-catalyst mixtures produced above,it may be desirable at times to modify the product by including othertypes of polyols and catalysts. For example, it may be desirable toinclude other known catalysts for this reaction, such as, for example,polyamines, tin octoate, dibutyl tin dilaurate, n-alkyl morpholines,diazabicyclooctane, and the like. Other polyols that may be includedinclose those possessing at least 2 to 6 hydroxyl groups. Suitableexamples include, among others polyethylene glycol, polyesters asglycol-terephthalate, glycol-succinate, tetramethyleneglycol-adipate orother hydroxy-terminated linear esters. Other polyols may be glycerol,1,2,6-hexanetriol, 1,3,6-octanetriol, a polyethylene ether derivative ofglycerol or 1,2,6-hexanetriol, erythritol, pentaerythritol, mannitol,sorbitol, alpha-methyl glucose and sucrose. Other polyols include thoseprepared by reacting an alkylene oxide such as ethylene oxide, propyleneoxide, 1,2-butylene oxide, styrene oxide, epichlorohydrin, glycidol andmixtures thereof with a polyhydric alcohol such as carbohydrates,glycerol, hexanetriol, petaerythritol sorbitol, methyl glucoside,sucrose, and the like. In addition, alkylene oxide adducts of certainamines, such as, for example, any of the aforementioned oxides withamines such as ethylene diamine, aminoethylpiperazine, etc. may also beused. Hydroxy-terminated polyesters are also useful in preparing theproducts of the invention. These include those prepared by reactingdibasic acids such as adipic acid, phthalic acid, terephthalic acid, anddiols or triols, such as diethylene glycol, glycerol, trimethylpropaneand the like.

Preferred polyols to be used include those obtained by reactingpolyalkylene oxides with polyhydric alcohols, the polyols obtained byreacting the alkylene oxides with polyamines and the polyols obtained byreacting polybasic acids with polyhydric alcohols to formhydroxy-terminated products.

The selection of the reactant components will vary depending upon thetype of product desired. In general when a flexible cellular product isdesired, the polyols should preferably have a functionality of fromabout 2 to 4 and a molecular weight of about 2000 to 6000. For rigidfoams, the functionality of the polyol is preferably from about 4 to 8and a molecular weight of about 300 to about 1200. For polyisocyanuratefoams the functionality of the polyol is preferably from about 2 to 8and the molecular weight varies from about 105 to 1000.

The amount of the polyisocyanate and the polyol-catalyst mixture to beused in making the polyurethane cellular products of the presentinvention may vary over a wide range. In general, the amount of thepolyisocyanate should be sufficient to react with all of the OH groupspresent in the polyol portion of the mixture and preferably in excessthereof. More preferably there is about 1 to 8 equivalents of theisocyanate groups per equivalent of OH groups. As noted above, anunexpected advantage of the use of the new polyol-catalyst systemsincludes their ability to bring about the incorporation of much largeramounts of isocyanurate linkages than possible heretofore. Coming underspecial consideration then would be the use of larger amounts of theisocyanates, such as, for example, from 2 to 5 equivalents of isocyanategroups per equivalent of OH.

When the polyol-catalyst mixture is added in the amount described above,the amount of catalyst present is sufficient to effect the desired rapidreaction.

Foams may be prepared by the so-called "one-shot" method or the"quasi-prepolymer" method. In the one-shot method, the ingredients aresimultaneously intimately mixed with each other to provide a foam by aone-step process. In accordance with the quasi-prepolymer method, aportion of the polyol compound is reacted in the absence of the catalystwith the polyisocyanate component. To prepare a foam, the remainingportion of the polyol is added and the two components are allowed toreact in the presence of catalystic systems such as those discussedabove and other appropriate additives. Usually a flexible foam isprepared by the one-shot method whereas rigid foams may be produced bythat method or the quasi-prepolymer method. Polyurethane orpolyisocyanurate elastomers, coatings, solid polymers, etc. may also beprepared by known techniques.

The polymers prepared with the new polyol-catalysts may be used for awide variety of end-uses. For example, the rigid, flexible,semi-flexible or semi-rigid type of polyurethane or polyisocyanuratefoams may be used for thermal insulation and as building materials andthe like. As specific examples, the cellular products of the inventioncan be employed as thermal barriers in the construction of fire walls,in the building of industrial and institutional structures, and asinsulating materials for high temperature pipelines and ovens, insupersonic aircraft and also as missile components.

To illustrate the preparation of the new polyol-catalyst compositionsand the new cellular products, the following examples are given. It isto be understood, however, that the examples are given only in the wayof illustration and are not to be regarded as limiting the invention inany way.

EXAMPLE I

To a 5-gallon kettle was added 10.0 lbs (0.0167 lb. mole) of an aqueous(24% water) Mannich base condensate, which was prepared fromnonylphenol, diethanolamine and aqueous 37% formaldehyde as described inU.S. Pat. No. 3,297,597. The condensate solution was heated to 110° C.to 115° C. and 6.0 lb (0.103 lb mole) propylene oxide was added. Afterdigesting the reaction mixture to constant pressure a water analysisgave 14.4% water present. An additional 1.0 lb propylene oxide wasadded, and after digestion showed a water concentration of 11.4%. Thewater and excess oxide were finally vacuum stripped to 5 mmm Hg/110° C.to give 14.25 lb of a dark red product, having the following analysis:

    ______________________________________                                        Hydroxyl number, mg. KOH/g.                                                                         638                                                     Total amine, meg./g.   2.3                                                    Viscosity (25° C.), cps                                                                      3,500                                                   Color (Gardner)       10-11                                                   pH (25% isopropanol:water)                                                                          10.6                                                    ______________________________________                                    

EXAMPLE II

To a 15 gallon reactor kettle was added 22.0 lb (0.10 lb mole) ofp-nonylphenol and 22.0 lb (0.21 lb mole) diethanolamine. Then 17.0 lb(0.21 lb mole) 37% aqueous formalin was added slowly while the kettletemperature was maintained between 30° and 40° C. After all the formalinwas added the kettle was heated to 110° C. and the reaction mixturedigested for four hours. After this period, the water concentration was23.9%.

While heating at 110° C. to 115° C., 35.0 lb (0.60 lb mole) propyleneoxide was slowly added. After a digestion period of two hours, the waterconcentration was 7.5%. Water and excess oxide were removed by vacuumstripping to 8 mm Hg/110° C. The product was a dark red liquid. Yieldwas 82 lbs.

    ______________________________________                                        Analysis:                                                                     ______________________________________                                        Hydrogen number, mg. KOH/g.                                                                         611                                                     Total amine, meg./g.  2.50                                                    Viscosity, cps (25° C.)                                                                      6,450                                                   Wt % water            0.02                                                    Color (Gardner)       12-13                                                   pH                    10.7                                                    ______________________________________                                    

EXAMPLE III

The procedure of Example II was used; however, the aqueous Mannichcondensate was prepared by admixing 11.0 lb, p-nonylphenol, 11.0 lbdiethanolamine and 8.5 lb 37% formalin, followed by a three hourdigestion period at 110° C.

The aqueous condensate was heated at 110° C. while 13.5 lb (0.307 lbmole) ethylene oxide was added. After digesting for one hour at 110° C.the mixture was stripped to a water concentration of 0.03%. Yield was36.3 lb of dark red, slightly viscous liquid.

    ______________________________________                                        Analysis:                                                                     ______________________________________                                        Hydroxyl no., mg. KOH/g.                                                                          557                                                       Total amine, meg/g. 2.84                                                      Viscosity (25° C.), cps                                                                    7,900                                                     Color (Gardner)     13-.4                                                     pH (25% isopropanol:water)                                                                        12.1                                                      ______________________________________                                    

EXAMPLE IV

To a 15-gallon kettle was added 14.9 lbs (0.10 lb mole) triethanolamine(99%) and 3.6 lb water. The resulting mixture was heated up to 110° to115° C. under nitrogen while 23.2 lbs (0.40 lb mole) propylene oxide wasslowly added. After a two hour digestion period at 10° C. to 115° C. thewater concentration was 6.28%.

The product was stripped in high vacuum to remove 4 to 5 lbs water andoxide. Yield was 38.0 lb of light, red-brown mobile liquid.

    ______________________________________                                        Analysis:                                                                     ______________________________________                                        Hydroxyl No.      580                                                         Total amine       5.4                                                         Viscosity (25° C.), cps                                                                  300                                                         Wt, % water       0.03                                                        Color             6-7                                                         pH                11.2                                                        ______________________________________                                    

EXAMPLE V

The procedure of Example II was repeated. However, the aqueous Mannichcondensate was prepared by reacting 26.4 lbs p-noylphenol, 26.4 lbsdiethanolamine and 20.2 lbs of 37% aqueous formaldehyde at 95°-100° C.for about five hours.

While heating at 100° C. the above condensate mixture was reacted with33.0 lb ethylene oxide and digesting to constant pressure over a onehour period. After vacuum stripping the mixture down to 5 mm Hg/100° C.87.3 lbs of a dark-red viscous product was obtained.

    ______________________________________                                        Analysis:                                                                     ______________________________________                                        Hydroxyl no.       575                                                        Total amine        2.8                                                        Viscosity (25° C.)                                                                        7,900                                                      Wt % water          0.16                                                      Color (Gardner)    12-13                                                      pH (isopropanol:water)                                                                           12.1                                                       ______________________________________                                    

EXAMPLE VI

To a 15-gallon reactor kettle was added 15.0 lb (0.10 lb mole)p-tertbutylphenol and 22.0 lb diethanolamine. Then 17.0 lb (0.21 mole)of 37% aqueous formaldehyde was added. After a four hour digestionperiod at 100°-110° C., the water concentration was 23.4%.

The aqueous condensate was heated at 110° C. while 35.0 lb (0.60 lbmole) propylene oxide was added slowly. After a one hour digestionperiod at 110° C. the water concentration was 10.6%.

The above mixture was finally vacuum stripped to 10 mm Hg/100° C. togive 74.6 lb of red, viscous liquid polyol.

    ______________________________________                                        Analysis:                                                                     ______________________________________                                        Hydroxyl number     640                                                       Total amine         2.76                                                      Viscosity, cps (25° C.)                                                                    6,800                                                     Water, wt %         0.052                                                     Color (Gardner)     10-11                                                     pH (25% isopropanol:water)                                                                        10.3                                                      ______________________________________                                    

EXAMPLE VII

To a one-liter stirred autoclave was added 195 g (1.0 mole)N-benzyldiethanolamine and 72 g (4.0 mole) water. The mixture was heatedto 100°-110° C. and 174 gram (3.0 moles) propylene oxide was added.After a short digestion period, the mixture was stripped in high vacuumto remove water and give 385 g. light yellow product.

    ______________________________________                                        Analysis:                                                                     ______________________________________                                        Hydroxyl number     544                                                       Total amine         2.38                                                      Viscosity (25° C.) cps                                                                     1,620                                                     Wt. % water         0.08                                                      Color (Gardner)     9-10                                                      pH (25% isopropanol/water)                                                                        10.2                                                      ______________________________________                                    

EXAMPLE VIII

The polyol-catalyst composition prepared in Example I was used toprepare a rigid foam. This was accomplished by adding 33.5 parts of thepolyol to 53.5 parts of Mondur MR, 0.5 parts silicone DC-193, 12.5 partsof fluorocarbon-11. The properties of the resulting foam are shown inTable I Components used in the reaction are identified as follows:

Thanol TR-380--an ethylene oxide adduct of aniline, see U.S. Pat. No.4,067,833

Trichloroethyl phosphate

Silicone DC-193--silicone-glycol copolymer

Freon R-11-B--trifluorochloromethane

Mondur MR--mixture of 50% diphenylmethane diisocyanate and 50% higherpolymers of similar structure, has a 32% NCO content and equivalentweight of 132.

EXAMPLES IX to XIV

The polyol-catalyst mixtures prepared in Examples I, 3, 4, 5, 6 and 7were used to prepare rigid polyurethane foams. The conditions andresults are shown in Table I.

As can be seen, the use of the new polyol-catalyst mixtures gaveproducts having high isocyanate indices, excellent heat temperatures andgood insulation properties. In addition, there was excellentcompatability of the polyol-catalyst mixtures with the other ingredientsand the rate of reaction could be easily controlled. The polyol-catalystmixtures also imparted no amine odor to the final product.

                                      TABLE NO. I                                 __________________________________________________________________________    RIGID FOAM DATA                                                                               Ex. VIII                                                                             Ex. IX Ex. X  Ex. XI Ex. XII                                                                              Ex. XIII                   __________________________________________________________________________    Formulation, pbw.                                                             Polyol Ex. 1    33.5   33.5   21.4   16.7   --     --                         Polyol Ex. 3    --     --     --     --     8      7                          THANOL ® TR-380                                                                           --     --     --     --     12     13                         Tri(chloroethyl)phosphate                                                                     --     --     --     6.0    --     --                         Silicone DC-193 0.5    0.5    0.5    0.5    0.5    0.5                        Freon R-11-B    12.5   12.5   12.5   12.5   12.5   12.5                       Mondur MR       53.5   53.5   65.6   64.3   67.0   67.0                       Isocyanate Index                                                                              1.05   1.05   2.0    2.5    3.5    3.6                        Butler Chimney Test                                                           Flame height, inches                                                                          --     --     --     --     6.33   6.5                        Time (sec.) to extinguish                                                                     --     --     --     --     10.83  10.5                       % weight retained                                                                             --     --     --     --     92.7   92.8                       Foam Appearance Good   Good   Good   Good   Good   Good                       Initial Surface Friability                                                                    None   V.     Yes    V.     V.     Slight                                            slight        slight slight                            Reaction rate                                                                 Cream time, sec.                                                                              27     27     30     36     9      16                         Tack free time, sec.                                                                          50     50     70     75     35     45                         Rise time, sec. 85     75     120    110    55     68                         Physical Properties                                                           Density, pcf.   1.92   1.99   2.02   2.00   2.13   2.10                       Comp. str., psi. parallel                                                                     45.20  43.74  38.46  34.52  37.76  36.08                      perp.           17.40  19.22  14.86  13.53  12.47  12.15                      Heat dist. temp., °C.                                                                  180    187    211    195    >225   >225                       Closed cells %  94.41  92.20  92.62  90.74  91.95  91.32                      K-factor        0.114  0.126  0.126  0.126  0.119  0.126                      Dimensional stability                                                                         ΔV ΔW ΔL                                                           ΔV ΔW ΔL                                                           ΔV ΔW ΔL                                                           ΔV ΔW ΔL                                                           ΔV ΔW                                                                    ΔV ΔW                                                             ΔL                   1 week -20° F.                                                                         -2 +1 -1                                                                             -3 +1 -2                                                                             -4  0 -2                                                                             -2  0 -2                                                                             -4 +1 -2                                                                             -3 +1 -2                   1 week 200° F.                                                                         +4 -1 +2                                                                             +2 -1 +2                                                                             +3 -1 +2                                                                             +3 -3 +2                                                                             +5 -2 +3                                                                             +6 -2 +3                   1 week 158° F., 100% R.H.                                                              +4 -2 +3                                                                             +2 -1 +1                                                                             +2 -2 +1                                                                             +3 -4 +3                                                                             +4 -3 +3                                                                             +5 -4 +3                   Tumbling friability (% wt. loss)                                                              9.4    24.6   25.2   44.2   31.7   30.3                       __________________________________________________________________________

                                      TABLE NO. II                                __________________________________________________________________________                    Ex. XIV                                                                            Ex. XV Ex. XVI                                                                              Ex. XVII                                                                             Ex. XVIII                                                                            Ex. XIX                      __________________________________________________________________________    Formulation, pbw.                                                             Polyol (Ex. IV) 20.0 --     --     --     --     --                           Polyol (Ex. V)  --   10     --     --     --     --                           Polyol (Ex. II) --   --     20     --     --     --                           Polyol (Ex. VI) --   --     --     20     17.4   --                           Polyol (Ex. VII)                                                                              --   --     --     --     --     20.0                         THANOL ® TR-380                                                                           --   10     --     --     --     --                           Tri(chloroethyl)phosphate                                                                     --   --     --     --     6.0    --                           Silicone DC-193 0.5  0.5    0.5    0.5    0.5    0.5                          Freon R-11-B    12.5 12.5   12.5   12.5   12.5   12.5                         Mondur MR       67.0 67.0   67.0   67.0   63.6   67.0                         Isocyanate Index                                                                              2.4  2.65   2.3    2.2    2.4    2.6                          Butler Chimney Test                                                           Flame height, inches                                                                          --   5.25   --     --     6.3    --                           Time (sec.) to extinguish                                                                     --   10     --     --     13.3   --                           % weight retained                                                                             --   93.6   --     --     89.3   --                           Foam Appearance Poor Good   Good   Good   Good   Poor                         Initial Surface Friability                                                                    Shrunk                                                                             V. slight                                                                            Yes    Yes    None   Shrunk                       Reaction Rate                                                                 Cream time, sec.                                                                              32   6      30     30     25     67                           Tack free time, sec.                                                                          190  21     60     67     62     --                           Rise time, sec. 134  40     90     105    100    --                           Physical Properties                                                           Density, pcf.        2.05   2.00   2.02   1.97                                Comp. str., psi. parallel                                                                          35.54  38.28  41.22  26.51                               perp.                11.78  15.01  16.10  19.1                                Heat dist. temp, °C.                                                                        >225   215    220    200                                 Closed cells %       92.1   92.6   93.0   89.0                                K-factor             0.120  0.129  0.123  0.158                               Dimensional stability                                                                              ΔV ΔW ΔL                                                           ΔV ΔW ΔL                                                           ΔV ΔW ΔL                                                           ΔV ΔW ΔL          1 week -20° F.                                                                              -12 +1 +8                                                                            -3 +1 -2                                                                             -2  0 -2                                                                              0 +1  0                            1 week 200° F.                                                                              +8 -1 +5                                                                             +4 -1 +2                                                                             +4 -1 +2                                                                             +5 +3 +3                            1 week 158° F., 100% R.H.                                                                   +8 -2 +5                                                                             +3 -1 +2                                                                             +2 -3 +2                                                                             +3 -5 +4                            Tumbling friability (% wt. loss)                                                                   23.8   43.8   27.5   64.1                                __________________________________________________________________________

What is claimed is:
 1. A process for preparing cellular polyurethaneproducts by reacting the polyol-catalyst mixture prepared by a processwhich comprises heating a Mannich base compound with water and anepoxide and subsequently removing the water from the reaction mixture,said Mannich based compound being the reaction product of a phenol, analkanolamine and formaldehyde with a polyisocyanate and a volatileblowing agent.
 2. A process as in claim 1 wherein the reaction mixturealso contains a foam stabilizer, flame retardant and filler.
 3. Aprocess as in claim 1 wherein the polyisocyanate is an aromaticpolyisocyanate having from 2 to 6 isocyanate groups.
 4. A process as inclaim 1 wherein the polyisocyanate equivalents to polyol equivalentsvary from 1:1 to 8:1.
 5. A process as in claim 1 wherein thepolyisocyanate is a methylene-bridged polyphenyl polyisocyanate.